U.S. patent number 10,941,090 [Application Number 16/797,707] was granted by the patent office on 2021-03-09 for processes for producing trifluoroiodomethane using metal trifluoroacetates.
This patent grant is currently assigned to Honeywell International Inc.. The grantee listed for this patent is Honeywell International Inc.. Invention is credited to Christian Jungong, Haiyou Wang, Terris Yang.
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United States Patent |
10,941,090 |
Jungong , et al. |
March 9, 2021 |
Processes for producing trifluoroiodomethane using metal
trifluoroacetates
Abstract
The present disclosure provides a process for producing
trifluoroiodomethane. The process includes providing a metal
trifluoroacetate, an iodine source, a metal catalyst, and a
solvent, and reacting the metal trifluoroacetate and the iodine
source in the presence of the metal catalyst and the solvent to
produce trifluoroiodomethane. The metal catalyst includes at least
one selected from the group of ferrous chloride and zinc (II)
iodide.
Inventors: |
Jungong; Christian (Depew,
NY), Wang; Haiyou (Amherst, NY), Yang; Terris (East
Amherst, NY) |
Applicant: |
Name |
City |
State |
Country |
Type |
Honeywell International Inc. |
Morris Plains |
NJ |
US |
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|
Assignee: |
Honeywell International Inc.
(Charlotte, NC)
|
Family
ID: |
1000005409034 |
Appl.
No.: |
16/797,707 |
Filed: |
February 21, 2020 |
Prior Publication Data
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Document
Identifier |
Publication Date |
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US 20200283359 A1 |
Sep 10, 2020 |
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Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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62813500 |
Mar 4, 2019 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C07C
19/16 (20130101); C07C 17/361 (20130101); C07C
2523/06 (20130101); C07C 2523/745 (20130101) |
Current International
Class: |
C07C
17/361 (20060101); C07C 19/16 (20060101) |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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101219925 |
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Jul 2008 |
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CN |
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102992943 |
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Mar 2013 |
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CN |
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Other References
Hongying et al, Preparation of trifluoroiodomethane, CN 102992943
machine translation, Jun. 2015. cited by examiner .
Exner et al., "Iron-Catalyzed Decarboxylation of Trifluoroacetate
and Its Application to the Synthesis of Trifluoromethyl
Thioethers", Chem. Eur. J., 2015, vol. 21, pp. 17220-17223. cited
by applicant .
Haszeldine, R. N. (1951). 124. The Reactions of Metallic Salts of
Acids with Halogens. Part I. The Reaction of Metal
Trifluoroacetates with Iodine, Bromine, and Chlorine. Journal of
the Chemical Society, pp. 584-587. cited by applicant .
International Search Report and Written Opinion received for PCT
Patent Application No. PCT/US2020/020731, dated Jun. 29, 2020, 11
pages. cited by applicant.
|
Primary Examiner: Parsa; Jafar F
Attorney, Agent or Firm: Faegre Drinker Biddle & Reath
LLP
Parent Case Text
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a U.S. Nonprovisional Application which claims
priority to Provisional Application No. 62/813,500, filed Mar, 4,
2019, which is incorporated herein by reference in its entirety.
Claims
What is claimed is:
1. A process for producing trifluoroiodomethane (CF.sub.3I), the
process comprising: providing a metal trifluoroacetate, an iodine
source, a metal catalyst and a solvent; and reacting the metal
trifluoroacetate, the iodine source, and the metal catalyst in the
presence of the solvent to produce trifluoroiodomethane, wherein
the metal catalyst includes at least one selected from the group of
ferrous chloride and zinc (II) iodide.
2. The process of claim 1, wherein in the providing step, a mole
ratio of the metal trifluoroacetate to the iodine source is from
about 0.1:1 to about 2.0:1.
3. The process of claim 1, wherein in the providing step, the
catalyst may be provided for the reaction at a mole percent of the
metal trifluoroacetate of from about 0.5% to about 50%.
4. The process of claim 1, wherein in the providing step, the metal
trifluoroacetate is selected from the group of lithium
trifluoroacetate, potassium trifluoroacetate, sodium
trifluoroacetate, calcium trifluoroacetate, magnesium
trifluoroacetate, and combinations thereof.
5. The process of claim 1, wherein in the providing step, the
iodine source is selected from the group of iodine, iodine
monochloride, iodine pentafluoride, and combinations thereof.
6. The process of claim 1, wherein in the providing step, the
solvent comprises less than about 500 ppm by volume of water.
7. The process of claim 1, wherein in the providing step, the
solvent is selected from the group of an ionic liquid, a polar
aprotic solvent, and combinations thereof.
8. The process of claim 7, wherein the solvent is selected from the
group of imidazolium salts, caprolactamium hydrogen sulfate,
sulfolane, N,N-dimethylacetamide, N-methyl-2-pyrrolidone (NMP),
dimethyl sulfone, and combinations thereof.
9. The process of claim 8, wherein the solvent consists of
sulfolane.
10. The process of claim 1, wherein the metal catalyst comprises
ferrous chloride.
11. The process of claim 1, wherein in the reacting step, the metal
trifluoroacetate, the iodine source, and the solvent are at a
temperature from about 100.degree. C. to about 250.degree. C.
12. A process for producing trifluoroiodomethane (CF.sub.3I), the
process comprising: mixing a metal trifluoroacetate, an iodine
source, a metal catalyst, and a solvent; and heating the metal
trifluoroacetate, the iodine source, the metal catalyst, and the
solvent to react the metal trifluoroacetate and iodine source to
produce trifluoroiodomethane and a metal salt, wherein the metal
catalyst includes at least one selected from the group of ferrous
chloride and zinc (II) iodide.
13. The process of claim 12, further including separating the
trifluoroiodomethane from the metal salt.
14. The process of claim 12, wherein the process is a continuous
process.
15. The process of claim 12, wherein the process is a batch
process.
16. The process of claim 12, wherein the metal trifluoroacetate is
selected from the group of lithium trifluoroacetate, potassium
trifluoroacetate, sodium trifluoroacetate, calcium
trifluoroacetate, magnesium trifluoroacetate, and combinations
thereof.
17. The process of claim 12, wherein the solvent is selected from
the group of an ionic liquid, a polar aprotic solvent, and
combinations thereof.
18. The process of claim 17, wherein the solvent is selected from
the group of imidazolium salts, caprolactamium hydrogen sulfate,
sulfolane, N,N-dimethylacetamide, N-methyl-2-pyrrolidone (NMP),
dimethyl sulfone, and combinations thereof.
19. The process of claim 12, wherein in the metal catalyst
comprises ferrous chloride.
20. The process of claim 12, wherein in the reacting step, the
metal trifluoroacetate, the iodine source, and the solvent are at a
temperature from about 100.degree. C. to about 250.degree. C.
Description
FIELD
The present disclosure relates to processes for producing
trifluoroiodomethane (CF.sub.3I). Specifically, the present
disclosure relates to methods to produce trifluoroiodomethane from
metal trifluoroacetates.
BACKGROUND
Trifluoroiodomethane (CF.sub.3I) is a useful compound in commercial
applications, as a refrigerant or a fire suppression agent, for
example. Trifluoroiodomethane is an environmentally acceptable
compound with a low global warming potential and low ozone
depletion potential. Trifluoroiodomethane can replace more
environmentally damaging materials.
Methods of preparing trifluoroiodomethane from metal
trifluoroacetates and iodine are known. For example, R. N
Haszeldine, Reactions of metallic salts of acids with halogens.
Part I. The reaction of metal trifluoroacetates with iodine,
bromine, and chlorine, 124 J. Chem. Soc. (1951) discloses the
decarboxylative iodination of metal trifluoroacetates
(CF.sub.3COOM) in the presence of iodine to make
trifluoroiodomethane. The process by R. N Haszeldine is performed
in a sealed tube or stainless-steel autoclave in which the metal
trifluoroacetate and elemental iodine are heated together in the
absence of a solvent to make trifluoroiodomethane. In another
example, Chinese Patent CN102992943B discloses the reaction of
metal trifluoroacetates and elemental iodine in the liquid phase to
produce trifluoroiodomethane, carbon dioxide, and metal iodide.
Yet in other examples, metal catalysts have been used in the liquid
phase to promote trifluoromethylation reactions of aromatic- and
alkyl halides, using metal trifluoroacetates as the
trifluoromethylating agents. For instance, Chun Song et al,
Progress in Copper-Catalyzed Trfifluoromethylation, 14 Beilstein J.
Org. Chem, 2018, 155-181 discloses the trifluoromethylation of aryl
iodides using potassium trifluoroacetate as the
trifluoromethylating agent. In the process, two mole equivalents of
copper (I) iodide with respect to the amount of aryl iodide were
used. Notably, in other examples, copper (I) iodide was only used
in sub-stoichiometric amounts. While the use of the metal catalyst
will reduce reaction time, assure completion of the reaction, and
produce high yields, copper (I) iodide is a relatively expensive
catalyst.
Thus, there is a need to develop catalysts that are more efficient
and economical in the production of trifluoroiodomethane from metal
trifluoroacetates.
SUMMARY
The present disclosure provides processes for producing
trifluoroiodomethane by reacting a metal trifluoroacetate with an
iodine source in the presence of a metal catalyst including ferrous
chloride (FeCl.sub.2) and/or zinc (II) iodide (ZnI.sub.2).
In one form thereof, the present disclosure provides a process for
producing trifluoroiodomethane. The process includes providing a
metal trifluoroacetate, an iodine source, a metal catalyst, and a
solvent, and reacting the metal trifluoroacetate and iodine source
in the presence of the metal catalyst and the solvent to produce
trifluoroiodomethane. The metal catalyst includes at least one
selected from the group of ferrous chloride and zinc (II)
iodide.
In one form thereof, the present disclosure provides a process for
producing trifluoroiodomethane. The process includes mixing a metal
trifluoroacetate, an iodine source, a metal catalyst, and a
solvent; and heating the metal trifluoroacetate, the iodine source,
the metal catalyst, and the solvent to react the metal
trifluoroacetate and iodine source to produce trifluoroiodomethane
and a metal salt. The metal catalyst includes at least one selected
from the group of ferrous chloride and zinc (II) iodide.
The above mentioned and other features of the disclosure, and the
manner of attaining them, will become more apparent and will be
better understood by reference to the following description of
embodiments taken in conjunction with the accompanying
drawings.
DESCRIPTION OF THE DRAWING
The FIGURE illustrates the pressure in a reactor over time for
batch syntheses of trifluoroiodomethane corresponding to Examples
1-3 below. The FIGURE compares a synthesis using a ferrous chloride
catalyst to a synthesis using a copper (I) iodide catalyst, and to
a synthesis using no catalyst.
DETAILED DESCRIPTION
The present disclosure provides a liquid phase process for the
manufacture of trifluoroiodomethane (CF.sub.3I) from a metal
trifluoroacetate (CF.sub.3COOM) and an iodine source, such as
iodine (I.sub.2), iodine monochloride (ICl), or iodine
pentafluoride (IF.sub.5) by decarboxylative iodination according to
Equation 1 below:
CF.sub.3COOM+I-X.sub.(z).fwdarw.CF.sub.3I+CO.sub.2+MX Eq. 1: where
M is an alkali metal, such as lithium, potassium, or sodium, or an
alkaline earth metal, such as calcium or magnesium; X is a halogen,
such as fluorine, chlorine, bromine, or iodine; and Z is an
integer. Thus, the metal trifluoroacetate may be at least one
selected from the group of lithium trifluoroacetate, potassium
trifluoroacetate, sodium trifluoroacetate, calcium
trifluoroacetate, and magnesium trifluoroacetate.
The reaction is carried out with a metal catalyst. The use of a
metal catalyst provides advantages in the production of
trifluoroiodomethane. In general, copper(I) iodide (Cul) catalyzed
trifluoromethylation reactions involving metal trifluoroacetates
are believed to function through a single-electron transfer
mechanism. However, it is generally used in stoichiometric amounts.
The high cost of copper(I) iodide, in conjunction with the amount
needed, make it desirable to find other catalysts capable of
promoting decarboxylative iodination of metal trifluoroacetates for
the formation of CF.sub.3I.
Catalysts useful for carrying out the reaction in the liquid phase
have been found to include ferrous chloride (FeCl.sub.2) and zinc
(II) iodide (ZnI.sub.2). Ferrous chloride and zinc (II) iodide are
commercially available. Ferrous chloride, in particular, is more
abundantly available compared to copper (I) iodide and
significantly less expensive. For example, ferrous chloride and
zinc (II) iodide may be obtained from Sigma-Aldrich Corp., St.
Louis, Mo.
The catalyst may be provided for the reaction at a mole percent of
the metal trifluoroacetate as low as about 0.5%, about 1%, about
2%, about 5%, about 10%, about 15%, about 20% or about 25%, or as
high as about 30%, about 35%, about 40%, about 45%, or about 50%,
or within any range defined between any two of the foregoing
values, such as about 5% to about 50%, about 2% to about 45%, about
5% to about 40%, about 10% to about 35%, about 15% to about 30%,
for example. Preferably, the catalyst is provided at a mole percent
of the metal trifluoroacetate from about 0.5% to about 35%. More
preferably, the catalyst is provided at a mole percent of the metal
trifluoroacetate from about 10% to about 30%. Most preferably, the
catalyst is provided at a mole percent of the metal
trifluoroacetate about 25%.
The relatively low cost of ferrous chloride and zinc (II) iodide
compared to copper (I) iodide, in conjunction with the lower,
non-stoichiometric amounts required result in significantly more
efficient and economical methods for producing trifluoroiodomethane
from metal trifluoroacetates and iodine sources.
The reaction is carried out in a solvent. Solvents useful for
carrying out the reaction in the liquid phase include
N,N-dimethylformamide, dimethyl sulfoxide, ionic liquids, polar
aprotic solvents, and combinations thereof. Examples of ionic
liquids include imidazolium salts and caprolactamium hydrogen
sulfate. Examples of polar aprotic solvents with high boiling
points include sulfolane, N,N-dimethylacetamide,
N-methyl-2-pyrrolidone (NMP), and dimethyl sulfone.
The solvent is substantially free of water. Substantially free of
water means that the amount of water in the solvent is less than
about 500 parts per million (ppm), about 300 ppm, about 200 ppm,
about 100 ppm, about 50 ppm, about 30 ppm, about 20 ppm, or about
10 ppm, or less than any value defined between any two of the
foregoing values. The foregoing ppm values are by weight of the
solvent and any water. Preferably, the amount of water in the
solvent is less than about 100 ppm. More preferably, the amount of
water in the solvent is less than about 50 ppm. Most preferably,
the amount of water in the solvent is less than about 10 ppm.
Metal trifluoroacetates are readily available in commercial
quantities. For example, potassium trifluoroacetate and iodine may
be obtained from Sigma-Aldrich Corp., St. Louis, Mo. The solvents
may also be readily obtained in commercial quantities. For example,
sulfolane may be also be obtained from Sigma-Aldrich Corp., St.
Louis, Mo.
The reactants may be provided for the reaction at a mole ratio of
metal trifluoroacetate to iodine source as low as about 0.1:1,
about 0.2:1, about 0.3:1, about 0.4:1, about 0.5:1, about 0.6:1,
about 0.7:1, about 0.8:1, about 0.9:1, about 0.95:1, about 0.99:1,
or about 1:1, or as high as about 1.01:1, about 1.05:1, about
1.1:1, about 1.2:1, about 1.3:1, about 1.4:1, about 1.5:1, about
1.6:1, about 1.8:1, or about 2.0:1, or within any range defined
between any two of the foregoing values, such as about 0.1:1 to
about 2.0:1, about 0.5:1 to about 1.5:1, about 0.6:1 to about
1.4:1, about 0.7:1 to about 1.3:1, about 0.8:1 to about 1.2:1,
about 0.9:1 to about 1.1:1, about 0.95:1 to about 1.05:1, about
0.99:1 to about 1.01:1, about 1:1 to about 2:1, about 0.8:1 to
about 1.5:1, or about 0.95:1 to about 1.2:1, for example.
Preferably, the mole ratio of metal trifluoroacetate to the iodine
source is from about 0.8:1 to about 1.5:1. More preferably, the
mole ratio of metal trifluoroacetate to the iodine source is from
about 1:1 to about 1.2:1. Most preferably, the mole ratio of metal
trifluoroacetate to the iodine source is about 1:1.
The reaction may be conducted a temperature as low as about
100.degree. C., about 110.degree. C., about 120.degree. C., about
130.degree. C., about 140.degree. C., about 150.degree. C., about
160.degree. C., or about 170.degree. C., or at a temperature as
high as about 180.degree. C., about 190.degree. C., about
200.degree. C., about 210.degree. C., about 220.degree. C., about
230.degree. C., about 240.degree. C., or about 250.degree. C., or
within any range defined between any two of the foregoing values,
such as about 100.degree. C. to about 250.degree. C., about
110.degree. C. to about 240.degree. C., about 120.degree. C. to
about 230.degree. C., about 130.degree. C. to about 220.degree. C.,
about 140.degree. C. to about 210.degree. C., about 150.degree. C.
to about 200.degree. C., about 160.degree. C. to about 190.degree.
C., about 170.degree. C. to about 180.degree. C., about 120.degree.
C. to about 130.degree. C., about 110.degree. C. to about
180.degree. C., or about 120.degree. C. to about 250.degree. C.,
for example. Preferably, the reactants are heated to a temperature
from about 100.degree. C. to about 250.degree. C. More preferably,
the reactants are heated to a temperature from about 110.degree. C.
to about 220.degree. C. Most preferably, the reactants are heated
to a temperature of about 120.degree. C. to about 200.degree.
C.
Pressure is not critical. Convenient operating pressures may range
from about 10 KPa to about 4,000 KPa, and preferably around ambient
pressure, or about 100 KPa to about 250 KPa.
The reaction is carried out in a liquid phase reactor. The liquid
phase reactor may be a semi-batch or continuously stirred tank
reactor (CSTR). The reaction may be carried out as a batch process
or as a continuous process.
The volatile products of the reaction, including the
trifluoroiodomethane, may be condensed and collected, thus
separating the trifluoroiodomethane from the non-volatile metal
salt byproduct.
The composition of the volatile organic products of the reaction
may be measured as by gas chromatography (GC) and gas
chromatography-mass spectroscopy (GC-MS) analyses. Graph areas
provided by the GC analysis for each of the volatile organic
compounds may be combined to provide a GC area percentage (GC area
%) of the total volatile organic compounds for each of the volatile
organic compounds as a measurement of the relative concentrations
of the volatile organic compounds produced in the reaction.
While this invention has been described as relative to exemplary
designs, the present invention may be further modified within the
spirit and scope of this disclosure. Further, this application is
intended to cover such departures from the present disclosure as
come within known or customary practice in the art to which this
invention pertains.
As used herein, the phrase "within any range defined between any
two of the foregoing values" literally means that any range may be
selected from any two of the values listed prior to such phrase
regardless of whether the values are in the lower part of the
listing or in the higher part of the listing. For example, a pair
of values may be selected from two lower values, two higher values,
or a lower value and a higher value.
EXAMPLES
Example 1
Decarboxylatiye Iodination without Catalyst
In this Example, the manufacture of trifluoroiodomethane from
potassium trifluoroacetate (CF.sub.3COOK) and elemental iodine is
demonstrated for comparison purposes. Potassium trifluoroacetate in
an amount of 20 g and elemental iodine in an amount of 38 g were
added to a 300-mL reactor from Parr Instrument Company, Moline,
Ill. The reactor was equipped with a condenser. The reactor was
pressure tested to 300 psig, and then evacuated. Sulfolane in an
amount of 60 mL was added to the reactor to form a reactant mixture
having a mole ratio of potassium trifluoroacetate to elemental
iodine of about 0.98:1. The reactants and the solvent were obtained
from Sigma-Aldrich Corp., St. Louis, Mo and used without further
purification.
The reactant mixture was heated to about 175.degree. C. No catalyst
was used in the reaction. Volatile gaseous products and byproducts
were produced as the reaction proceeded. The pressure in the
reactor was measured as the reaction progressed. The pressure in
the reactor over time is shown in the FIGURE. The volatile gases
exiting the condenser were collected in a product collection
cylinder cooled in dry ice.
The composition of the organic compounds in the volatile gases
collected in the product collection cylinder was measured by gas
chromatography (GC). Graph areas provided by the GC analysis for
each of the organic compounds were combined to provide a GC area
percentage (GC area %) of the total organic compounds for each of
the organic compounds as a measurement of the relative
concentrations of the organic compounds. The results are shown in
the Table below.
Example 2
Decarboxylatiye Iodination using a Cul Catalyst
In this Example, the manufacture of trifluoroiodomethane from
potassium trifluoroacetate (CF.sub.3COOK) and elemental iodine in
the presence of a copper (I) iodide (Cul) catalyst is demonstrated
for comparison purposes. Potassium trifluoroacetate in an amount of
20 g, copper (I) iodide in an amount of 6.2 g (25 mol %) and iodine
(I.sub.2) in an amount of 36.7 g were added to a 300-mL reactor
from Parr Instrument Company, Moline, Ill. The reactor was equipped
with a condenser. The reactor was pressure tested to 300 psig, and
then evacuated. Sulfolane in an amount of 60 mL was added to the
reactor to form a reactant mixture having a mole ratio of potassium
trifluoroacetate to elemental iodine of about 0.91:1. The reactants
and the solvent were obtained from Sigma-Aldrich Corp., St. Louis,
Mo. and used without further purification. The copper (I) iodide,
in powder form, was obtained from Sigma-Aldrich Corp., St. Louis,
Mo. and used without further purification.
The reactant mixture was heated to about 175.degree. C. Volatile
gaseous products and byproducts were produced as the reaction
proceeded. The pressure in the reactor was measured as the reaction
progressed. The pressure in the reactor over time is shown in the
FIGURE. The volatile gases exiting the condenser were collected in
a product collection cylinder cooled in dry ice.
The composition of the organic compounds in the volatile gases
collected in the product collection cylinder was measured by gas
chromatography (GC). Graph areas provided by the GC analysis for
each of the organic compounds were combined to provide a GC area
percentage (GC area %) of the total organic compounds for each of
the organic compounds as a measurement of the relative
concentrations of the organic compounds. The results are shown in
the Table below.
Example 3
Decarboxvlative Iodination using an FeCl.sub.2 Catalyst
In this Example, the manufacture of trifluoroiodomethane from
potassium trifluoroacetate (CF.sub.3COOK) and elemental iodine in
the presence of a ferrous chloride (FeCl.sub.2) catalyst is
demonstrated. Potassium trifluoroacetate in an amount of 20 g,
ferrous chloride in an amount of 4.2 g (25 mol %), and iodine
(I.sub.2) in an amount of 36.7 g were added to a 300-mL reactor
from Parr Instrument Company, Moline, Ill. The reactor was equipped
with a condenser. The reactor was pressure tested to 300 psig, and
then evacuated. Sulfolane in an amount of 60 mL was added to the
reactor to form a reactant mixture having a mole ratio of potassium
trifluoroacetate to elemental iodine of about 0.91:1. The reactants
and the solvent were obtained from Sigma-Aldrich Corp., St. Louis,
Mo. and used without further purification. Ferrous chloride, in
powder form, was obtained from Sigma-Aldrich Corp., St. Louis, Mo.
and used without further purification.
The reactant mixture was heated to about 175.degree. C. Volatile
gaseous products and byproducts were produced as the reaction
proceeded. The volatile gases exiting the condenser were collected
in a product collection cylinder cooled in dry ice.
The composition of the organic compounds in the volatile gases
collected in the product collection cylinder was measured by gas
chromatography (GC). Graph areas provided by the GC analysis for
each of the organic compounds were combined to provide a GC area
percentage (GC area %) of the total organic compounds for each of
the organic compounds as a measurement of the relative
concentrations of the organic compounds. The results are shown in
the Table below.
As shown in the Table below, the use of a ferrous chloride catalyst
results in higher selectivity for trifluoroiodomethane with reduced
production of the byproduct trifluoromethane (CHF.sub.3) when
compared to the reaction run with no catalyst or with copper(I)
iodide as the catalyst. As shown in the FIGURE, the ferrous
chloride catalyst promoted the reaction to an extent comparable to
that of the copper (I) iodide catalyst. The potassium
trifluoroacetate is hygroscopic and readily absorbs moisture from
the surrounding. The formation of CHF.sub.3 is attributed to the
presence of moisture in the reaction vessel from the potassium
trifluoroacetate.
TABLE-US-00001 TABLE CF.sub.3I CHF.sub.3 Other Catalyst (GC area %)
(GC area %) (GC area %) none 62.85% 35.35% 1.79% CuI 75.61% 22.20%
2.19% FeCl.sub.2 76.25% 19.86% 3.89%
ASPECTS
Aspect 1 is a process for producing trifluoroiodomethane
(CF.sub.3I), the process comprising providing a metal
trifluoroacetate, an iodine source, a metal catalyst and a solvent;
and reacting the metal trifluoroacetate, the iodine source, and the
metal catalyst in the presence of the solvent to produce
trifluoroiodomethane, wherein the metal catalyst includes at least
one selected from the group of ferrous chloride and zinc (II)
iodide.
Aspect 2 is the process of Aspect 1, wherein in the providing step,
a mole ratio of the metal trifluoroacetate to the iodine source is
from about 0.1:1 to about 2.0:1.
Aspect 3 is the process of Aspect 1, wherein in the providing step,
a mole ratio of the metal trifluoroacetate to the iodine source is
from about 0.8:1 to about 1.5:1.
Aspect 4 is the process of Aspect 1, wherein in the providing step,
a mole ratio of the metal trifluoroacetate to the iodine source is
from about 1.1:1 to about 1.2:1.
Aspect 5 is the process of Aspect 1, wherein in the providing step,
a mole ratio of the metal trifluoroacetate to the iodine source is
about 1:1.
Aspect 6 is the process of any of Aspects 1-5, wherein in the
providing step, the catalyst may be provided for the reaction at a
mole percent of the metal trifluoroacetate of from about 0.5% to
about 50%.
Aspect 7 is the process of any of Aspects 1-5, wherein in the
providing step, the catalyst may be provided for the reaction at a
mole percent of the metal trifluoroacetate of from about 0.5% to
about 35%.
Aspect 8 is the process of any of Aspects 1-5, wherein in the
providing step, the catalyst may be provided for the reaction at a
mole percent of the metal trifluoroacetate of from about 10% to
about 30%.
Aspect 9 is the process of any of Aspects 1-5, wherein in the
providing step, the catalyst may be provided for the reaction at a
mole percent of the metal trifluoroacetate of from about 20% to
about 30%.
Aspect 10 is the process of any of Aspects 1-9, wherein in the
providing step, the metal trifluoroacetate is at least one selected
from the group of lithium trifluoroacetate, potassium
trifluoroacetate, sodium trifluoroacetate, calcium
trifluoroacetate, and magnesium trifluoroacetate.
Aspect 11 is the process of any of Aspects 1-9, wherein in the
providing step, the metal trifluoroacetate is selected from the
group consisting of lithium trifluoroacetate, potassium
trifluoroacetate, sodium trifluoroacetate, calcium
trifluoroacetate, magnesium trifluoroacetate, and combinations
thereof.
Aspect 12 is the process of any of Aspects 1-9, wherein in the
providing step, the metal trifluoroacetate is at least one selected
from the group of potassium trifluoroacetate and sodium
trifluoroacetate.
Aspect 13 is the process of any of Aspects 1-9, wherein in the
providing step, the metal trifluoroacetate consists of potassium
trifluoroacetate.
Aspect 14 is the process of any of Aspects 1-13, wherein in the
providing step, the iodine source is at least one selected from the
group of iodine, iodine monochloride, and iodine pentafluoride.
Aspect 15 is the process of Aspect 14, wherein the iodine source
consists of iodine monochloride.
Aspect 16 is the process of Aspect 14, wherein the iodine source
consists of iodine.
Aspect 17 is the process of any of Aspects 1-16, wherein in the
providing step, the organic solvent comprises less than about 500
ppm by volume of water.
Aspect 18 is the process any of Aspects 1-16, wherein in the
providing step, the organic solvent comprises less than about 100
ppm by volume of water.
Aspect 19 is the process any of Aspects 1-16, wherein in the
providing step, the organic solvent comprises less than about 50
ppm by volume of water.
Aspect 20 is the process any of Aspects 1-16, wherein in the
providing step, the organic solvent comprises less than about 10
ppm by volume of water.
Aspect 21 is the process of any of Aspects 25-40, wherein in the
providing step, the organic solvent is at least one selected from
the group of an ionic liquid and a polar aprotic solvent.
Aspect 22 is the process of Aspect 21, wherein the organic solvent
is at least one selected from the group of imidazolium salts,
caprolactamium hydrogen sulfate, sulfolane, N,N-dimethylacetamide,
N-methyl-2-pyrrolidone (NMP), and dimethyl sulfone.
Aspect 23 is the process of Aspect 22, wherein the organic solvent
consists of sulfolane.
Aspect 24 is the process of any of Aspects 1-23, wherein the metal
catalyst comprises ferrous chloride.
Aspect 25 is the process of any of Aspects 1-23, wherein the metal
catalyst consists of ferrous chloride.
Aspect 26 is the process of any of Aspects 1-23, wherein the metal
catalyst comprises zinc (II) iodide.
Aspect 27 is the process of any of Aspects 1-23, wherein the metal
catalyst consists of zinc (II) iodide.
Aspect 28 is the process of any of Aspects 1-27, wherein in the
reacting step, the metal trifluoroacetate, the iodine source, and
the solvent are at a temperature from 100.degree. C. to 250.degree.
C.
Aspect 29 is the process of any of Aspects 1-27, wherein in the
reacting step, the metal trifluoroacetate, the iodine source, and
the solvent are at a temperature from about 100.degree. C. to about
250.degree. C.
Aspect 30 is the process of any of Aspects 1-27, wherein in the
reacting step, the metal trifluoroacetate, the iodine source, and
the solvent are at a temperature from about 110.degree. C. to about
220.degree. C.
Aspect 31 is the process of any of Aspects 1-27, wherein in the
reacting step, the metal trifluoroacetate, the iodine source, and
the solvent are at a temperature from about 120.degree. C. to about
200.degree. C.
Aspect 32 is the process for producing trifluoroiodomethane
(CF.sub.3I), the process comprising mixing a metal
trifluoroacetate, an iodine source, a metal catalyst, and a
solvent; and heating the metal trifluoroacetate, the iodine source,
the metal catalyst, and the solvent to react the metal
trifluoroacetate and iodine source to produce trifluoroiodomethane
and a metal salt, wherein the metal catalyst includes at least one
selected from the group of ferrous chloride and zinc (II)
iodide.
Aspect 33 is the process of Aspect 32, further including separating
the trifluoroiodomethane from the metal salt.
Aspect 34 is the process of either of Aspects 32 or 33, wherein the
process is a continuous process.
Aspect 35 is the process of either of Aspects 32 or 33, wherein the
process is a batch process.
Aspect 36 the process of any of Aspects 32-35, wherein a mole ratio
of the metal trifluoroacetate to the iodine source is from about
0.1:1 to about 2.0:1.
Aspect 37 is the process of Aspect 1, wherein a mole ratio of the
metal trifluoroacetate to the iodine source is from about 0.8:1 to
about 1.5:1.
Aspect 38 is the process of Aspect 1, wherein a mole ratio of the
metal trifluoroacetate to the iodine source is from about 1.1:1 to
about 1.2:1.
Aspect 39 is the process of Aspect 1, wherein a mole ratio of the
metal trifluoroacetate to the iodine source is about 1:1.
Aspect 40 is the process of any of Aspects 1-5, wherein the
catalyst may be provided for the reaction at a mole percent of the
metal trifluoroacetate of from about 0.5% to about 50%.
Aspect 41 is the process of any of Aspects 1-5, wherein the
catalyst may be provided for the reaction at a mole percent of the
metal trifluoroacetate of from about 0.5% to about 35%.
Aspect 42 is the process of any of Aspects 1-5, wherein the
catalyst may be provided for the reaction at a mole percent of the
metal trifluoroacetate of from about 10% to about 30%.
Aspect 43 is the process of any of Aspects 1-5, wherein the
catalyst may be provided for the reaction at a mole percent of the
metal trifluoroacetate of from about 20% to about 30%.
Aspect 44 is the process of any of Aspects 1-9, wherein the metal
trifluoroacetate is at least one selected from the group of lithium
trifluoroacetate, potassium trifluoroacetate, sodium
trifluoroacetate, calcium trifluoroacetate, and magnesium
trifluoroacetate.
Aspect 45 is the process of any of Aspects 1-9, wherein the metal
trifluoroacetate is at least one selected from the group of lithium
trifluoroacetate, potassium trifluoroacetate, sodium
trifluoroacetate, calcium trifluoroacetate, and magnesium
trifluoroacetate.
Aspect 46 is the process of any of Aspects 1-9, wherein the metal
trifluoroacetate is a least one selected from the group of
potassium trifluoroacetate, and sodium trifluoroacetate.
Aspect 47 is the process of any of Aspects 1-9, wherein the metal
trifluoroacetate consists of potassium trifluoroacetate.
Aspect 48 is the process of any of Aspects 1-13, wherein the iodine
source is at least one selected from the group of iodine, iodine
monochloride, and iodine pentafluoride.
Aspect 49 is the process of Aspect 14, wherein the iodine source
consists of iodine monochloride.
Aspect 50 is the process of Aspect 14, wherein the iodine source
consists of iodine.
Aspect 51 is the process of any of Aspects 1-16, wherein the
organic solvent comprises less than about 500 ppm by volume of
water.
Aspect 52 is the process any of Aspects 1-16, wherein the organic
solvent comprises less than about 100 ppm by volume of water.
Aspect 53 is the process any of Aspects 1-16, wherein the organic
solvent comprises less than about 50 ppm by volume of water.
Aspect 54 is the process any of Aspects 1-16, wherein the organic
solvent comprises less than about 10 ppm by volume of water.
Aspect 55 is the process of any of Aspects 25-40, wherein the
organic solvent is at least one selected from the group of an ionic
liquid and a polar aprotic solvent.
Aspect 56 is the process of Aspect 21, wherein the organic solvent
is at least one selected from the group of imidazolium salts,
caprolactamium hydrogen sulfate, sulfolane, N,N-dimethylacetamide,
N-methyl-2-pyrrolidone (NMP), and dimethyl sulfone.
Aspect 57 is the process of Aspect 22, wherein the organic solvent
consists of sulfolane.
Aspect 58 is the process of any of Aspects 1-23, wherein the metal
catalyst comprises ferrous chloride.
Aspect 59 is the process of any of Aspects 1-23, wherein the metal
catalyst consists of ferrous chloride.
Aspect 60 is the process of any of Aspects 1-23, wherein the metal
catalyst comprises zinc (II) iodide.
Aspect 61 is the process of any of Aspects 1-23, wherein the metal
catalyst consists of zinc (II) iodide.
Aspect 62 is the process of any of Aspects 1-27, wherein the metal
trifluoroacetate, the iodine source, and the solvent are heated to
a temperature from 100.degree. C. to 250.degree. C.
Aspect 63 is the process of any of Aspects 1-27, wherein the metal
trifluoroacetate, the iodine source, and the solvent are heated to
a temperature from about 100.degree. C. to about 250.degree. C.
Aspect 64 is the process of any of Aspects 1-27, wherein the metal
trifluoroacetate, the iodine source, and the solvent are heated to
a temperature from about 110.degree. C. to about 220.degree. C.
Aspect 65 is the process of any of Aspects 1-27, wherein the metal
trifluoroacetate, the iodine source, and the solvent are heated to
a temperature from about 120.degree. C. to about 200.degree. C.
* * * * *